Adhesive film and sealing product for organic electronic device using same

ABSTRACT

Provided are an adhesive film, and an organic electronic device (OED) encapsulation product using the same. Dimensional stability, lifespan, and durability may be enhanced even when a panel of an organic electronic device is large-sized and formed as a thin film by controlling dimensional tolerance and edge angular tolerance of the adhesive film, thereby ensuring long-term reliability, and process yields may be enhanced when the adhesive film is applied to an automation process.

This application is a Continuation of U.S. application Ser. No.14/527,182, filed Oct. 29, 2014, which is a Continuation Bypass ofInternational Application No. PCT/KR2013/007054, filed on Aug. 5, 2013,and claims priority to Korean Application Nos. 10-2012-0085427, filed onAug. 3, 2012 and 10-2013-0092549, filed on Aug. 5, 2013, all of whichare hereby incorporated by reference in their entireties as if fully setforth herein.

1. FIELD OF THE INVENTION

The present invention relates to an adhesive film and an encapsulationproduct of an organic electronic device (OED) using the same.

2. DISCUSSION OF RELATED ART

An organic electronic device refers to a device including an organicmaterial layer generating exchange of charges using holes and electrons,and may include a photovoltaic device, a rectifier, a transmitter, andan organic light emitting diode (OLED).

An organic light emitting diode, which is a representative organicelectronic device, consumes less power and has a higher response speedthan conventional light sources, and is preferable as a thin displaydevice or light. In addition, the organic light emitting diode hasexcellent space utilization, and thus is expected to be applied invarious fields including all kinds of portable devices, monitors,notebook computers, and TVs.

To expand compatibility and use of the organic light emitting diode, themost important problem is durability. Organic materials and metalelectrodes included in the organic light emitting diode are very easilyoxidized by external factors such as moisture, and a product includingthe organic light emitting diode is very sensitive to environmentalfactors. Therefore, there are demands for developing encapsulants whichcan effectively prevent permeation of moisture, reduce damages to theorganic electronic device, and ensure long-term reliability.

SUMMARY OF THE INVENTION

The present invention is directed to providing an adhesive film and anorganic electronic device encapsulation product using the same.

In one aspect, the present invention provides an adhesive filmencapsulating an organic electronic device including a curable adhesivelayer including a curable resin, and a dimensional tolerance (d) or edgeangular tolerance (x) of the adhesive film satisfies Equation 1 or 2.

d=|d _(f) −d _(i)|<800 μm

x=|x _(f) −x _(i)|<0.05 degrees  [Equation 1]

Here, d_(i) is a length of a longer side or shorter side of the adhesivefilm at an optional i point, and d_(f) is a length of a longer side orshorter side of the adhesive film at a point of 2 weeks or more afterthe optional i point.

In another aspect, the present invention provides an encapsulationproduct of an organic electronic device, which includes a substrate; anorganic electronic device formed on the substrate; and the adhesive filmencapsulating the organic electronic device that covers an entiresurface of the organic electronic device.

Effect

Adhesive films according to exemplary embodiments of the presentinvention can have enhanced dimensional stability, lifespan, anddurability even when a panel of an organic electronic device islarge-sized and formed as a thin film by controlling dimensionaltolerance and edge angular tolerance of the adhesive film, therebyensuring long-term reliability, and have enhanced process yields whenapplied to an automation process.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Hereinafter, exemplary embodiments of the present invention will bedescribed in further detail. In addition, to describe the presentinvention, detailed descriptions of related known conventional functionsor components will be omitted.

The term “organic electronic device (OED)” refers to a material ordevice having a structure including an organic material layer generatingexchange of charges using holes and electrons between a pair ofelectrodes facing each other, which may be, for example, a photovoltaicdevice, a rectifier, a transmitter, and an organic light emitting diode,but the present invention is not limited thereto. In one example of thepresent invention, the organic electronic device may be an organic lightemitting diode.

In the specification, the curable adhesive may be an adhesive that canbe maintained in a solid or semi-solid state at room temperature, attacha planar plate without bubbles due to flowability when heat is applied,and firmly fix a target with the adhesive when a curing reaction isterminated.

The adhesive film according to an exemplary embodiment of the presentinvention encapsulates an organic electronic device, the adhesive filmincludes a curable adhesive layer including a curable resin, and adimensional tolerance (d) or edge angular tolerance (x) of the adhesivefilm satisfies Equation 1 or 2.

d=|d _(f) −d _(i)|<800 μm

x=|x _(f) −x _(i)|<0.05 degrees  [Equation 1]

Here, d_(i) is a length of a longer side or shorter side of the adhesivefilm at an optional i point, and d_(f) is a length of a longer side orshorter side of the adhesive film at a point of 2 weeks or more afterthe optional i point.

In the specification, the optional i point refers to an optional pointwithin two hours after the adhesive film is manufactured.

It is important that the adhesive film ensures long-term reliability toincrease process yields when applied to an automation process inencapsulation of the organic electronic device. To ensure the long-termreliability, the dimensional tolerance and edge angular tolerance of theadhesive film may be controlled, and in order to do this, the adhesivefilm according to exemplary embodiments of the present invention may bestored at −10 to 10° C., −5 to 10° C., 0 to 10° C., or 2 to 5° C.

The dimensional tolerance of the adhesive film refers to a differencebetween a dimension of the film at an optional i point before storage ina refrigerator and a dimension of the film after storage in arefrigerator, and the dimension refers to a length of a longer side(horizontal side) or a shorter side (vertical side) of the adhesivefilm, and the tolerances of the respective dimensions are within a rangeof less than ±800 μm.

The edge angular tolerance of the adhesive film refers to change betweenan angle of an edge of the film at an optional i point before storage ina refrigerator and an angle of an edge of the film after storage in arefrigerator. An edge angle of an ideal adhesive film may be 90 degrees,altered by a wooden pattern to cut the adhesive film, and changedaccording to storage. However, to be applied to an automatedencapsulation process for an organic electronic device, an angulartolerance of each edge of the adhesive film is less than ±0.05 degrees,and preferably less than ±0.03 degrees. It is preferable that all edgesnecessarily have an angular tolerance as described above.

The dimensional tolerance and angular tolerance of each edge of theadhesive film is necessary to be applied to a process regardless of thedimension of the adhesive film. However, recently, for a large-sizedorganic electronic device, a minimum size of the adhesive film may be 15inches.

When the dimensional tolerance and angular tolerance of the adhesivefilm is controlled within the above range, defects of the product causedby dimensional change may be reduced, the lifespan of the organicelectronic device may be maintained longer, and durability may beenhanced.

The adhesive film may have a viscosity at room temperature of 10⁶ or 10⁷dyne/cm² or more. The term “room temperature” used herein may refer to atemperature, which is neither increased nor decreased, for example,approximately 15 to 35° C., particularly, approximately 20 to 25° C.,and more particularly, approximately 25° C. The viscosity may bemeasured using an advanced rheometric expansion system (ARES). When theviscosity of the curable adhesive is controlled within the above range,high processability in the process of encapsulating the organicelectronic device can be obtained, and a planar plane can beencapsulated to a uniform thickness. In addition, unlike a liquidadhesive, the curable adhesive can prevent physical or chemical damageto the organic electronic device by drastically reducing problems ofcontraction and generation of a volatile gas which may occur due tocuring of a resin. In the present invention, as long as the adhesive ismaintained in a solid or semi-solid state at room temperature, the upperlimit of the viscosity is not particularly limited, and for example, inconsideration of the processability, the viscosity may be controlledwithin the range of approximately 10⁹ dyne/cm² or less.

In addition, since the adhesive film has the moisture resistance, andstructurally allows the substrate to be adhered to an upper substrate, amanufacturing process is easily performed in the manufacture of a panelof the organic electronic device, the manufacturing process is simplesince a separate passivation process can be omitted, and anencapsulation thickness of the organic electronic device is reduced tocontribute to formation of a thin panel.

In exemplary embodiments of the present invention, a curable resin thatcan be used may have a water vapor transmission rate (WVTR) in a curedstate of 50 g/m²·day or less, and preferably, 30 g/m²·day, 20 g/m²·day,or 15 g/m²·day or less. The term “cured state of a curable resin” refersto a state converted into a state in which the curable resin hasconstant components of the moisture absorbent and filler, and serves asa structural adhesive when the curable resin is cured or crosslinked bybeing used alone or by reacting with other components such as a curingagent and then applied to an encapsulant. The WVTR may be measured in athickness direction of the cured product at 38° C. and relative humidityof 100% after the curable resin is cured and the cured product is formedin a film having a thickness of 80 μm. In addition, the WVTR may bemeasured according to ASTM F1249.

When the WVTR is controlled within the above range, the permeation ofmoisture, vapor, or oxygen into an organic electronic deviceencapsulation product may be effectively inhibited, and an effect ofintroducing a moisture reactive absorbent may be exhibited.

In one exemplary embodiment of the present invention, as the WVTR in thecured state of the resin is decreased, the encapsulation structure has abetter performance. The lower limit of the WVTR is not particularlylimited.

A specific kind of curable resin that can be used in the presentinvention is not particularly limited, and for example, may includevarious heat-curable or photocurable resins, which are known in the art.The term “heat-curable resin” refers to a resin that can be curedthrough suitable application of heat or aging, and the term“photocurable resin” refers to a resin that can be cured by theradiation of electromagnetic waves. In addition, in the category of theelectromagnetic waves, microwaves, IR rays, UV rays, X rays, and γ rays,and particle beams such as α-particle beams, proton beams, neutronbeams, and electron beams may be included. As an example of thephotocurable resin, a cationic photocurable resin may be used. Thecationic photocurable resin refers to a resin that can be cured bycationic polymerization or cationic curing induced by the radiation ofelectromagnetic waves. In addition, the curable resin may be adual-curable resin including both of heat-curing and photocuringcharacteristics.

A specific kind of the curable resin is not particularly limited, aslong as the curable resin has the above-described characteristics. Forexample, the curable resin may be a resin that can be cured to exhibitadhesive characteristics, which includes a resin including at least oneheat-curable functional group such as a glycidyl group, an isocyanategroup, a hydroxyl group, a carboxyl group, or an amide group, or atleast one functional group that can be cured by the radiation ofelectromagnetic waves such as an epoxide group, a cyclic ether group, asulfide group, an acetal group, or a lactone group. In addition, aspecific kind of the resin may include an acryl resin, a polyesterresin, an isocyanate resin, or an epoxy resin, but the present inventionis not limited thereto.

As the curable resin, an aromatic or aliphatic, and linear or branchedepoxy resin may be used. In one exemplary embodiment of the presentinvention, an epoxy resin containing at least two functional groups andhaving an epoxy equivalent of 180 to 1,000 g/eq may be used. As theepoxy resin having the above epoxy equivalent is used, characteristicssuch as adhesive performance and a glass transition temperature of thecured product may be effectively maintained. Such an epoxy resin may beone or a mixture of at least two of a cresol novolac epoxy resin, abisphenol A-type epoxy resin, a bisphenol A-type novolac epoxy resin, aphenol novolac epoxy resin, a tetrafunctional epoxy resin, abiphenyl-type epoxy resin, a triphenol methane-type epoxy resin, analkyl-modified triphenol methane epoxy resin, a naphthalene-type epoxyresin, a dicyclopentadiene-type epoxy resin, and adicyclopentadiene-modified phenol-type epoxy resin.

In the present invention, as an example, an epoxy resin including acyclic structure in a molecular structure, and particularly, an epoxyresin including an aromatic group (e.g., a phenyl group), may be used.When the epoxy resin includes an aromatic group, a cured product mayhave excellent thermal and chemical stabilities and low WVTR, therebyenhancing reliability of the organic electronic device encapsulationstructure. A specific example of the aromatic group-containing epoxyresin that can be used in the present invention may be, but is notlimited to, one or a mixture of at least two of a biphenyl-type epoxyresin, a dicyclopentadiene-type epoxy resin, a naphthalene-type epoxyresin, a dicyclopentadiene-modified phenol-type epoxy resin, acresol-based epoxy resin, a bisphenol-based epoxy resin, a xyloc-basedepoxy resin, a multifunctional epoxy resin, a phenol novolac epoxyresin, a triphenolmethane-type epoxy resin, and an alkyl-modifiedtriphenolmethane epoxy resin.

As the epoxy resin, a silane-modified epoxy resin, for example, asilane-modified epoxy resin having an aromatic group may be used.

As the silane-modified epoxy resin, for example, a reaction product ofat least one of the epoxy resins described above and a silane compoundmay be used. Here, the silane compound may be, for example, a compoundrepresented by Formula 1.

D _(n)SiX_((4-n))  [Formula 1]

In Formula 1, D is a vinyl group, an epoxy group, an amino group, anacryl group, a methacryl group, a mercapto group, an alkoxy group, or anisocyanate group, or an alkyl group substituted with at least one of thefunctional groups described above, X is hydrogen, an alkyl group, ahalogen, an alkoxy group, an aryl group, an aryloxy group, an acyloxygroup, an alkylthio group, or an alkyleneoxythio group, and n is anumber of 1 to 3.

In the compound of Formula 1, the functional group “D” may react with afunctional group included in an epoxy resin, thereby forming asilane-modified epoxy resin.

For example, when the functional group is an amino group, the aminogroup may react with an epoxy group of the epoxy resin, thereby forminga “—CH(OH)—CH₂—NH—” bond, and thus the silane compound may be introducedinto the epoxy group.

In addition, when the functional group “D” is an isocyanate group or analkoxy group, a silane compound may be introduced by reacting thefunctional group “D” with an epoxy resin including a hydroxyl (OH)group, for example, a bisphenol-type epoxy resin such as a bisphenolF-type epoxy resin, a bisphenol F-type novolac epoxy resin, a bisphenolA-type epoxy resin, or a bisphenol A-type novolac epoxy resin.

In Formula 1, as the alkyl group, an alkyl group having 1 to 20 carbonatoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms,or 1 to 4 carbon atoms may be used. The alkyl group may be a linear,branched, or cyclic alkyl group.

In Formula 1, as the halogen atom, fluorine (F), chlorine (Cl), bromine(Br), or iodine (I) may be used.

In addition, in Formula 1, as the alkoxy group, an alkoxy group having 1to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4carbon atoms may be used. The alkoxy group may be a linear, branched, orcyclic alkoxy group.

In addition, in Formula 1, the aryl group or the aryl group included inthe aryloxy group may include a so-called aralkyl group or arylalkylgroup as well as the aryl group. For example, the aryl group may referto a monovalent residue derived from a compound including at least onebenzene ring or a structure in which at least two benzene rings arelinked or condensed, or a derivative thereof. The aryl group may be, forexample, an aryl group having 6 to 25, 6 to 21, 6 to 18, or 6 to 12carbon atoms. The aryl group may be, for example, a phenyl group, adichlorophenyl group, a chlorophenyl group, a phenylethyl group, aphenylpropyl group, a benzyl group, a tolyl group, a xylyl group, or anaphthyl group, and preferably, a phenyl group.

In addition, in Formula 1, the acyloxy group may be an acyloxy grouphaving 1 to 20 carbon atoms, 1 to 16 carbon atoms, or 1 to 12 carbonatoms.

In addition, in Formula 1, the alkylthio group may be an alkylthio grouphaving 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms,1 to 8 carbon atoms, or 1 to 4 carbon atoms, and the alkyleneoxythiogroup may be an alkyleneoxythio group having 1 to 20 carbon atoms, 1 to16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4carbon atoms.

The alkyl group, the alkoxy group, the aryl group, the acyloxy group,the alkylthio group, or the alkyleneoxythio group may be optionallysubstituted with at least one substituent. As the substituent, ahydroxyl group, an epoxy group, an alkyl group, an alkenyl group, analkynyl group, an alkoxy group, an acyl group, a thiol group, anacryloyl group, a methacryloyl group, an aryl group, or an isocyanategroup may be used, but the present invention is not limited thereto.

In Formula 1, the functional group “D” may be, for example, an alkoxygroup, an amino group, or an isocyanate group among the above-describedfunctional groups.

In addition, in Formula 1, the functional group “X” may be, for example,at least one, two or more, or three halogen atoms, alkoxy groups,aryloxy groups, acyloxy groups, alkylthio groups, or alkyleneoxythiogroups, and preferably alkoxy groups.

The silane-modified epoxy resin may be, for example, an epoxy resin towhich a silane compound is introduced in an amount of approximately 0.1to 10 parts by weight, 0.1 to 9 parts by weight, 0.1 to 8 parts byweight, 0.1 to 7 parts by weight, 0.1 to 6 parts by weight, 0.1 to 5parts by weight, 0.1 to 4 parts by weight, 0.1 to 3 parts by weight, 0.3to 2 parts by weight, or 0.5 to 2 parts by weight relative to 100 partsby weight of the epoxy resin. In one example, the epoxy resin into whichthe silane compound is introduced may be an aromatic epoxy resin. Thearomatic epoxy resin may be, for example, a bisphenol-type epoxy resinsuch as a bisphenol F-type epoxy resin, a bisphenol F-type novolac epoxyresin, a bisphenol A-type epoxy resin, or a bisphenol A-type novolacepoxy resin.

As described above, when the epoxy resin structurally having a silanegroup by being modified with a silane is used, adhesiveness of theorganic electronic device to a glass substrate or an inorganic substratematerial is maximized, and a moisture barrier ability or durability andreliability may also be enhanced. A specific kind of the epoxy resin isnot particularly limited, and the resin may be easily obtained from, forexample, a manufacturer such as Kukdo Chemical Co., Ltd.

In the present invention, the curable resin may also be a styrene-basedresin, a polyolefin-based resin, a thermoplastic elastomer, apolyoxyalkylene-based resin, a polyester-based resin, a polyvinylchloride-based resin, a polycarbonate-based resin, apolyphenylenesulfide-based resin, a mixture of hydrocarbon, apolyamide-based resin, an acrylate-based resin, an epoxy-based resin, asilicon-based resin, a fluorine-based resin, or a mixture thereof.

Here, as the styrene-based resin, for example, astyrene-ethylene-butadiene-styrene block copolymer (SEBS), astyrene-isoprene-styrene block copolymer (SIS), anacrylonitrile-butadiene-styrene block copolymer (ABS), anacrylonitrile-styrene-acrylate block copolymer (ASA), astyrene-butadiene-styrene block copolymer (SBS), a styrene-basedhomopolymer, or a mixture thereof may be used. As the olefin-basedresin, for example, a high density polyethylene-based resin, a lowdensity polyethylene-based resin, a polypropylene-based resin, or amixture thereof may be used. The thermoplastic elastomer may be, forexample, an ester-based thermoplastic elastomer, an olefin-basedthermoplastic elastomer, or a mixture thereof. Among these, apolybutadiene resin or a polyisobutene resin may be used as theolefin-based thermoplastic elastomer. As the polyoxyalkylene-basedresin, for example, a polyoxymethylene-based resin, apolyoxyethylene-based resin, or a mixture thereof may be used. As thepolyester-based resin, for example, a polyethylene terephthalate-basedresin, a polybutylene terephthalate-based resin, or a mixture thereofmay be used. As the polyvinylchloride-based resin, for example,polyvinylidene chloride may be used. As the mixture of hydrocarbon, forexample, hexatriacotane or paraffin may be used. As the polyamide-basedresin, for example, nylon may be used. As the acrylate-based resin, forexample, polybutyl(meth)acrylate may be used. As the epoxy-based resin,for example, a bisphenol-type resin such as a bisphenol A-type resin, abisphenol F-type resin, a bisphenol S-type resin, and a hydrationproduct thereof; a novolac-type resin such as a phenolnovolac-type resinor a cresolnovolac-type resin; a nitrogen-containing cyclic resin suchas a triglycidylisocyanurate-type resin or a hydantoin-type resin; analicyclic resin; an aliphatic resin; an aromatic resin such as anaphthalene-type resin or a biphenyl-type resin; a glycidyl-type resinsuch as a glycidylether-type resin, a glycidylamine-type resin, or aglycidylester-type resin; a dicyclo-type resin such as adicyclopentadiene-type resin; an ester-type resin; an etherester-typeresin; or a mixture thereof may be used. As the silicon-based resin, forexample, polydimethylsiloxane may be used. In addition, as thefluorine-based resin, a polytrifluoroethylene resin, apolytetrafluoroethylene resin, a polychlorotrifluoroethylene resin, apolyhexafluoropropylene resin, a polyfluorinated vinylidene, apolyfluorinated vinyl, a polyfluorinated ethylenepropylene, or a mixturethereof may be used.

The listed resins may be grafted with, for example, maleic acidanhydride, copolymerized with another one of the listed resins or amonomer for preparing a resin, or modified by another compound. As anexample of the compound, a carboxyl-terminal butadiene-acrylonitrilecopolymer may be used.

In addition, the listed resins may include at least one functional groupor site that can be cured by heat such as a glycidyl group, anisocyanate group, a hydroxyl group, a carboxyl group, or an amide group,or at least one functional group or site that can be cured by radiationof active energy beams such as an epoxide group, a cyclic ether group, asulfide group, an acetal group, or a lactone group to exhibitadhesiveness after curing.

In one example, the curable resin may include a polyisobutene resin. Thepolyisobutene resin may have hydrophobicity, thereby exhibiting a lowWVTR and low surface energy. Particularly, as the polyisobutene resin,for example, a homopolymer of an isobutylene monomer; or a copolymer ofan isobutylene monomer and a different monomer that can be polymerizedtherewith may be used. Here, the monomer that can be polymerized withthe isobutylene monomer may include, for example, 1-butene, 2-butene,isoprene, or butadiene.

The curable adhesive layer may further include a moisture absorbent aswell as the curable resin. The term “moisture absorbent” may refer to amoisture-reactive absorbent which is a component capable of absorbing orremoving moisture or vapor input from an external environment through achemical reaction.

The moisture absorbent chemically reacts with vapor, moisture, or oxygeninput to an inside of the adhesive layer to absorb moisture or vapor. Aspecific kind of the moisture absorbent is not particularly limited, andthe moisture absorbent may be one or a mixture of at least two of ametal powder such as alumina, a metal oxide, a metal salt, andphosphorus pentoxide (P₂O₅).

Here, a specific example of the metal oxide may be phosphorus pentoxide(P₂O₅), lithium oxide (Li₂O), sodium oxide (Na₂O), barium oxide (BaO),calcium oxide (CaO), or magnesium oxide (MgO), the metal salt may be asulfate such as lithium sulfate (Li₂SO₄), sodium sulfate (Na₂SO₄),calcium sulfate (CaSO₄), magnesium sulfate (MgSO₄), cobalt sulfate(CoSO₄), gallium sulfate (Ga₂(SO₄)₃), titanium sulfate (Ti(SO₄)₂), ornickel sulfate (NiSO₄); a metal halide such as calcium chloride (CaCl₂),magnesium chloride (MgCl₂), strontium chloride (SrCl₂), yttrium chloride(YCl₃), copper chloride (CuCl₂), cesium fluoride (CsF), tantalumfluoride (TaF₅), niobium fluoride (NbF₅), lithium bromide (LiBr),calcium bromide (CaBr₂), cesium bromide (CeBr₃), selenium bromide(SeBr₄), vanadium bromide (VBr₃), magnesium bromide (MgBr₂), bariumiodide (BaI₂), or magnesium iodide (MgI₂); or a metal chlorate such asbarium perchlorate (Ba(ClO₄)₂) or magnesium perchlorate (Mg(ClO₄)₂), butthe present invention is not limited thereto.

The metal oxides may be blended into the composition in a state in whichthe moisture absorbent is suitably processed. For example, depending onthe kind of an organic electronic device to which the adhesive film isto be applied, the adhesive layer may be a thin film having a thicknessof 30 μm or less, and in this case, it may be necessary to perform agrinding process on the moisture absorbent. To grind the moistureabsorbent, a process with a 3-roll mill, bead mill, or ball mill may beused. In addition, when the adhesive film of the present invention isapplied to a top-emissive organic electronic device, transmittance ofthe adhesive layer is very important, and thus it is necessary todecrease the size of the moisture absorbent. Therefore, to be used insuch a use, the moisture absorbent is necessarily subjected to agrinding process.

The adhesive layer may include the moisture absorbent in an amount of 1to 100 parts by weight relative to 100 parts by weight of the curableresin. When the moisture absorbent is included in the above range, acrack in the film caused by volume expansion caused by a reactionbetween the moisture absorbent and moisture may be prevented, physicalor chemical damage may be prevented, and long-term reliability of theadhesive film may also be provided.

Unless particularly defined otherwise, the units “parts by weight” usedherein refer to a weight ratio between components.

When the range of a content of the moisture absorbent is controlled asdescribed above, a cured product may exhibit excellent moisture andvapor resistances, a thin film-type encapsulation structure may beformed, and an excellent moisture resistance may be exhibited.

The curable adhesive layer may further include a filler. The filler is akind of physical moisture absorbent that may extend a traveling path ofmoisture or vapor that permeates into an encapsulation structure toinhibit the permeation of moisture or vapor, thereby maximizing aresistance to moisture and vapor due to a matrix structure of a curableresin and through interaction with the moisture absorbent. A specifickind of filler that can be used in the present invention may be, but isnot limited to, one or a mixture of at least two selected from the groupconsisting of clay, talc, silica, zeolite, zirconia, titania, andmontmorillonite.

In addition, to increase binding efficiency between the filler and anorganic binder, a product whose surface is treated with an organicmaterial may be used as the filler, or a coupling agent may be furtheradded to the filler.

The curable adhesive layer may include the filler in an amount of 1 to50 or 1 to 20 parts by weight relative to 100 parts by weight of thecurable resin. As the content of the filler is controlled to 1 part byweight or more, a cured product having excellent moisture or vaporresistance and mechanical properties may be provided. In addition, asthe content of the filler is controlled to 50 parts by weight or less, acured product capable of being formed in a film type, and exhibitingexcellent moisture resistance even when formed in a thin film, may beprovided.

A specific kind of curing agent that can be used is not particularlylimited, and may be suitably selected according to the curable resinused or the kind of a functional group included in the resin. Forexample, when an epoxy resin is used as the curable resin in the presentinvention, a general curing agent for an epoxy resin known in the artmay be used as the curing agent, which may be, but is not limited to,one or a mixture of at least two of amine-based compounds,imidazole-based compounds, phenol-based compounds, phosphorus-basedcompounds, and acid anhydride-based compounds.

The curable adhesive layer may include the curing agent in an amount of1 to 20 or 1 to 10 parts by weight relative to 100 parts by weight ofthe curable resin. However, the content is only an example of thepresent invention. That is, the content of the curing agent may bechanged according to the kind and content of the curable resin orfunctional group, and a matrix structure or crosslinking density to berealized.

In addition, the kind of the initiator that can be used in the presentinvention, for example, a cationic photopolymerization initiator is notparticularly limited, and a known cationic photopolymerization initiatorsuch as an aromatic diazonium salt, an aromatic iodine aluminum salt, anaromatic sulfonium salt, or an iron-arene complex, and preferably, anaromatic sulfonium salt may be used, but the present invention is notlimited thereto.

In this case, for example, a content of the initiator may be included inan amount of 0.01 to 10 or 0.1 to 3 parts by weight relative to 100parts by weight of the curable resin. When the content of the cationicphotopolymerization initiator is excessively low, curing may not besufficiently performed, and when the content of the cationicphotopolymerization initiator is excessively high, the content of theionic material is increased after curing, thereby degrading durabilityof the adhesive, or degrading optical durability of the adhesive becauseof formation of a conjugate acid as the characteristic of the initiator.In addition, depending on a base, corrosion may occur, and inconsideration of this, a suitable content range may be selected.

The curable adhesive layer may further include a high molecular weightresin. When the composition is molded in a film or sheet shape, the highmolecular weight resin serves to improve moldability. In addition, thehigh molecular weight resin may serve as a high-temperature viscositycontroller to control flowability in the process.

The kind of high molecular weight resin that can be used in the presentinvention is not particularly limited as long as the resin has acompatibility with another component such as the curable resin. Aspecific kind of the high molecular weight resin that can be used maybe, but is not limited to, a resin having a weight average molecularweight of 20,000 or more, which is one or a mixture of at least two of aphenoxy resin, an acrylate resin, a high molecular weight epoxy resin, aultra-high molecular weight epoxy resin, a rubber containing a highpolarity functional group, and a reactive rubber containing a highpolarity functional group, but the present invention is not limitedthereto.

When the high molecular weight resin is included in the curable adhesivelayer, the content is controlled according to a desired physicalproperty, and is not particularly limited. For example, the highmolecular weight resin may be included in an amount of approximately200, 150, or 100 parts by weight or less relative to 100 parts by weightof the curable resin. As the content of the high molecular weight resinis controlled to 200 parts by weight or less, the compatibility of theresin with each component may be effectively maintained, and the resinmay also serve as an adhesive.

The adhesive film may further include an additive such as an additionalfiller to enhance durability of the cured product, a coupling agent toenhance mechanical strength and adhesive strength, a plasticizer, a UVstabilizer, and an antioxidant without an influence on the effects ofthe present invention.

The curable adhesive layer of the adhesive film may have asingle-layered structure, or a multi-layered structure having at leasttwo adhesive layers. When the adhesive film includes multi-layeredadhesive layers, more of the moisture absorbent may be contained inlayers farther from the organic electronic device.

The structure of the adhesive film of the present invention is notparticularly limited as long as the adhesive film includes the adhesivelayer. For example, the adhesive film may have a structure including abase or releasing film (hereinafter, referred to as a “first film”); andthe adhesive layer formed on the base or releasing film.

The adhesive film may further include a base or releasing film(hereinafter, referred to as a “second film”), which is formed on theadhesive layer.

A specific kind of the first film that can be used in the presentinvention is not particularly limited. In the present invention, as thefirst film, for example, a general polymer film in the art may be used.In the present invention, for example, as the base or releasing film, apolyethyleneterephthalate film, a polytetrafluoroethylene film, apolyethylene film, a polypropylene film, a polybutene film, apolybutadiene film, a vinylchloride copolymer film, a polyurethane film,an ethylene-vinyl acetate film, an ethylene-propylene copolymer film, anethylene-acrylic acid ethyl copolymer film, an ethylene-acrylic acidmethyl copolymer film, or a polyimide film may be used. In addition,suitable releasing treatment may be performed on one or both surfaces ofthe base or releasing film of the present invention. An example of areleasing agent used in the releasing treatment of the base film may bean alkyd-, silicon-, fluorine-, unsaturated ester-, polyolefin-, orwax-based agent, and among these, in terms of heat resistance, analkyd-, silicon-, or fluorine-based releasing agent is preferably used,but the present invention is not limited thereto.

In addition, the kind of the second film (hereinafter, also referred toas “cover film”) that can be used in the present invention is notparticularly limited, either. For example, in the present invention, asthe second film, in the above-described range of the first film, onethat is the same as or different from the first film may be used. Inaddition, in the present invention, suitable releasing treatment mayalso be performed on the second film.

A thickness of the base or releasing film as described above (the firstfilm) is not particularly limited, and may be suitably selectedaccording to application. For example, in the present invention, thethickness of the first film may be approximately 10 to 500 μm or 20 to200 μm. When the thickness of the film is controlled within the aboverange, transformation of the base film may be prevented, and economicfeasibility may be increased.

A thickness of the second film is not particularly limited, either. Inthe present invention, for example, the thickness of the second film maybe set to be the same as that of the first film. In addition, inconsideration of processability, the thickness of the second film may beset to be relatively smaller than that of the first film.

A thickness of the adhesive layer included in the adhesive film is notparticularly limited, and in consideration of a use of the film, thethickness of the adhesive layer may be suitably selected according tothe following conditions.

In exemplary embodiments of the present invention, a method ofmanufacturing the adhesive film described above is not particularlylimited. For example, the adhesive film may be manufactured by coating acoating solution including a composition of the above-described adhesivelayer on a base or releasing film (first operation); and drying thecoating solution coated in the first operation (second operation).

In the method of manufacturing the adhesive film according to thepresent invention, compressing a base or releasing film on the coatingsolution dried in the second operation (third operation) may be furtherincluded.

The first operation is to prepare a coating solution by dissolving ordispersing a composition of the above-described adhesive layer in asuitable solvent. In this operation, a content of the epoxy resinincluded in the coating solution may be suitably controlled according todesired moisture resistance and film moldability.

The kind of the solvent used in the preparation of the coating solutionis not particularly limited. However, when a drying time of the solventis excessively long, or drying of the solvent at a high temperature isnecessary, problems in terms of workability or durability of theadhesive film may occur, and thus it is preferable that a solvent havinga volatile temperature of 100° C. or less be used. In addition, inconsideration of the film moldability, a small amount of a solventhaving a volatile temperature beyond the above range may be mixed. As anexample of the solvent that can be used in exemplary embodiments of thepresent invention, one or a mixture of at least two of methylethylketone(MEK), acetone, toluene, dimethylformamide (DMF), methylcellosolve(MCS), tetrahydrofuran (THF), and N-methylpyrollidone (NMP) can be used,but the present invention is not limited thereto.

In the first operation, a method of coating the coating solution on thebase or releasing film is not particularly limited, and a known methodsuch as knife coating, roll coating, spray coating, gravure coating,curtain coating, comma coating, or lip coating may be used withoutlimitation.

The second operation is to form an adhesive layer by drying the coatingsolution coated in the first operation. That is, in the secondoperation, the adhesive layer may be formed by drying and removing asolvent by heating the coating solution coated on the film. Here, adrying condition is not particularly limited, and the drying may beperformed at 70 to 200° C. for 1 to 10 minutes.

In the method of manufacturing the adhesive film, following the secondoperation, compressing another base or releasing film on the adhesivelayer formed on the film may be further included as the third operation.

The third operation described above may be performed by compressinganother releasing or base film (a cover film or a second film) on thedried adhesive layer by a hot roll laminating or pressing process, aftercoating the adhesive layer. Here, the third operation may be performedby hot roll laminating in terms of probability and efficiency of acontinuous process, and here, the process may be performed atapproximately 10 to 100° C., and a pressure of approximately 0.1 to 10kgf/cm².

Another exemplary embodiment of the present invention provides anorganic electronic device encapsulation product including a substrate;an organic electronic device formed on the substrate; and theabove-described adhesive film encapsulating the organic electronicdevice, in which the adhesive film covers an entire surface of theorganic electronic device.

The organic electronic device encapsulation product may further includea protective layer to protect the organic electronic device between theadhesive film and the organic electronic device.

The organic electronic device encapsulation product may further includean encapsulation substrate above the adhesive film, and here, theadhesive film serves to adhere the encapsulation substrate to thesubstrate. In one exemplary embodiment of the present invention, theorganic electronic device may be an organic light emitting diode (OLED).

The organic electronic device encapsulation product has advantages of asimple process and a decrease in production costs. The organicelectronic device encapsulation product can also be used regardless of amethod of designing the organic electronic device, and provide excellentmechanical durability to the organic electronic device.

Still another exemplary embodiment of the present invention provides amethod of encapsulating an organic electronic device, which includesapplying an adhesive layer of the above-described adhesive film to asubstrate on which an organic electronic device is formed to cover anentire surface of the organic electronic device, and curing the adhesivelayer.

The application of the adhesive film to the organic electronic devicemay be performed by hot-roll laminating, hot pressing, or vacuumcompressing the adhesive film, but the present invention is notparticularly limited.

The application of the adhesive film to the organic electronic devicemay be performed at 50 to 90° C., and the curing operation may beperformed by heating in a range of 70 to 110° C., or radiating UV rays.

In addition, the method may further include attaching the adhesive filmto face an additional encapsulation material such as glass or metal.

The method of encapsulating an organic electronic device includesforming a transparent electrode on a substrate such as glass or apolymer film by a method such as vacuum deposition or sputtering, andforming an organic material layer on the transparent electrode. Theorganic material layer may include a hole injection layer, a holetransport layer, an emitting layer, an electron injection layer, and/oran electron transport layer. Subsequently, a second electrode is furtherformed on the organic material layer. Afterward, the above-describedadhesive film is applied to a top surface of the organic electronicdevice on the substrate to cover an entire surface of the organicelectronic device. Here, a method of applying the adhesive film is notparticularly limited, and may be a method of heating or compressing acover substrate (e.g., glass or a polymer film) to which theabove-described adhesive layer of the adhesive film is previouslytransfer-printed to a top surface of the organic electronic deviceformed on the substrate. In this operation, for example, when theadhesive film is transfer-printed on the cover substrate, theabove-described adhesive film may be transfer-printed on the coversubstrate using a vacuum press or vacuum laminator by applying heatafter a base or releasing film formed on the film is peeled off. In thisoperation, when a curing reaction of the adhesive film is performed in acertain range or more, cohesive strength or adhesive strength of theadhesive film may be decreased, thereby preferably controlling a processtemperature and a process time to approximately 100° C. or less andapproximately within 5 minutes, respectively. Similarly, even when thecover substrate on which the adhesive film is transfer-printed isheat-compressed to the organic electronic device, a vacuum press orvacuum laminator may be used. A temperature condition for this operationmay be set as described above, and a process time may be within 10minutes.

In addition, an additional curing process to the adhesive film to whichthe organic electronic device is compressed may be performed, and such acuring process (main curing) may be performed, for example, in a heatingchamber or UV chamber. A curing condition in the main curing may besuitably selected in consideration of stability of the organicelectronic device.

However, the above-described forming process is merely an example forencapsulating the organic electronic device, and thus a sequence of orcondition for the process may be freely changed. For example, thesequence of the transfer-printing and compressing processes may bechanged in such a manner that the above-described adhesive film istransfer-printed to the organic electronic device on the substrate,followed by compressing the cover substrate. In addition, after theprotective layer is formed on the organic electronic device, theadhesive film may be applied and then cured without the cover substrate.

Hereinafter, the present invention will be described in further detailwith reference to Examples according to the present invention andComparative Examples not according to the present invention, but thescope of the present invention is not limited to the following Examples.

Examples 1 to 3

1. Preparation of Adhesive Solution

A moisture absorbent solution was prepared by putting 70 g of CaO(Aldrich) as a moisture absorbent into methylethylketone at aconcentration of 30 wt %, and milled by a ball-mill process for 24hours. In addition, separately, 200 g of a silane-modified epoxy resin(KSR-177, Kukdo Chemical Co., Ltd.) and 150 g of a phenoxy resin (YP-50,Tohto Kasei Co., Ltd.) were put into a reaction vessel at roomtemperature, and diluted with methylethylketone. Afterward, an inside ofthe reaction vessel was substituted with nitrogen, and the preparedsolution was homogenized. The moisture absorbent solution preparedbeforehand was put into the homogenized solution, 4 g of an imidazole(Shikoku Chemicals Co., Ltd.) was added as a curing agent, and theresulting solution was stirred at a high speed for 1 hour, therebypreparing an adhesive solution.

2. Manufacture of Adhesive Film

An adhesive layer having a thickness of 15 μm was formed by coating theabove-prepared adhesive solution to a releasing surface of a releasingPET using a comma coater, and drying the resulting surface with a drierat 130° C. for 3 minutes, and the releasing PET was further compressedto a top surface of the adhesive layer.

3. Storage of Adhesive Film

The above-prepared adhesive film was kept in a freezer at a temperatureof 4° C. for 2, 4, and 8 weeks.

Comparative Examples 1 to 3

Adhesive films were prepared by the same methods as described inExamples 1 to 3, except that a storage temperature was changed to 20° C.in the storage of the adhesive film in Example 1.

Experimental Example 1: Measurement of Dimensional Tolerance

To investigate dimensional tolerance and edge angular tolerance of theadhesive films in Examples 1 to 3 and Comparative Examples 1 to 3,particularly, the adhesive films in Examples 1 to 3 and ComparativeExamples 1 to 3 were cut to a size of 1218 mm×692 mm (55 inches) beforestorage. Right after the cutting operation, lengths of longer andshorter sides and angles of respective edges were measured. Afterward,as described in Examples 1 to 3, lengths of longer and shorter sides andangles of respective edges of the adhesive films stored for 2, 4, and 8weeks, respectively, at 4° C. were measured. In addition, as describedin Comparative Examples 1 to 3, lengths of longer and shorter sides andangles of respective edges of the adhesive films stored for 2, 4, and 8weeks, respectively, at 20° C. were measured.

The lengths of the longer and shorter sides and the angles of therespective edges right after the cutting and the lengths of the longerand shorter sides and differences in the angles of the edges after thestorage are shown in Tables 1 and 2.

TABLE 1 Category Example 1 Example 2 Example 3 Dimensional tolerance−100 −120 −60 (μm) Edge angular tolerance −0.01 0 +0.01 (degrees)Comparative Comparative Comparative Example 1 Example 2 Example 3Dimensional tolerance −880 −950 −820 (μm) Edge angular tolerance −0.05−0.06 −0.05 (degrees)

As seen from above, it can be confirmed that when the adhesive films inExamples 1 to 3 according to exemplary embodiments of the presentinvention were stored at 4° C., the dimensional tolerance was less than±800 μm, and the edge angular tolerance was less than ±0.05 degrees.However, like the conventional adhesive film, as the storage time forstoring the film at room temperature of 20° C. is increased, it can beconfirmed that the dimensional tolerance and the edge angular tolerancewere high.

While the invention has been shown and described with reference tocertain exemplary embodiments thereof, it will be understood by thoseskilled in the art that various changes in form and details may be madetherein without departing from the scope of the invention as defined bythe appended claims.

1. An adhesive film encapsulating an organic electronic device OED,comprising: a curable adhesive layer comprising a curable resin, whereina dimensional tolerance (d) or edge angular tolerance (x) of theadhesive film satisfies Equation 1 or 2:d=|d _(f) −d _(i)|<800 μmx=|x _(f) −x _(i)|<0.05 degrees  [Equation 1] where d_(i) is a length ofa longer side or shorter side of the adhesive film at an optional ipoint, d_(f) is a length of a longer side or shorter side of theadhesive film at a point of 2 weeks or more after the optional i point,x_(i) is an angle of an edge of the adhesive film at an optional ipoint, and x_(f) is an angle of an edge of the adhesive film at a pointof 2 weeks or more after the optional i point.
 2. The adhesive filmaccording to claim 1, wherein the curable adhesive layer has a viscosityat room temperature of 10⁶ dyne/cm² or more.
 3. The adhesive filmaccording to claim 1, wherein the curable resin has a water vaportransmission rate (WVTR) in a cured state of 50 g/m²·day or less.
 4. Theadhesive film according to claim 1, wherein the curable resin is aheat-curable resin, a photocurable resin, or a dual-curable resin. 5.The adhesive film according to claim 1, wherein the curable resincomprises at least one curable functional group selected from the groupconsisting of a glycidyl group, an isocyanate group, a hydroxyl group, acarboxyl group, an amide group, an epoxide group, a cyclic ether group,a sulfide group, an acetal group, and a lactone group.
 6. The adhesivefilm according to claim 1, wherein the curable resin is an epoxy resincomprising a cyclic structure in a molecular structure.
 7. The adhesivefilm according to claim 1, wherein the curable resin is asilane-modified epoxy resin.
 8. The adhesive film according to claim 1,wherein the adhesive layer further comprises a moisture absorbent. 9.The adhesive film according to claim 8, wherein the moisture absorbentis alumina, a metal oxide, a metal salt, or phosphorus pentoxide. 10.The adhesive film according to claim 9, wherein the moisture absorbentis at least one selected from the group consisting of P₂O₅, Li₂O, Na₂O,BaO, CaO, MgO, Li₂SO₄, Na₂SO₄, CaSO₄, MgSO₄, CoSO₄, Ga₂(SO₄)₃, Ti(SO₄)₂,NiSO₄, CaCl₂, MgCl₂, SrCl₂, YCl₃, CuCl₂, CsF, TaF₅, NbF₅, LiBr, CaBr₂,CeBr₃, SeBr₄, VBr₃, MgBr₂, BaI₂, MgI₂, Ba(ClO₄)₂, and Mg(ClO₄)₂.
 11. Theadhesive film according to claim 8, wherein the adhesive layer comprisesthe moisture absorbent in an amount of 1 to 100 parts by weight relativeto 100 parts by weight of the curable resin.
 12. The adhesive filmaccording to claim 1, wherein the adhesive layer further comprises afiller.
 13. The adhesive film according to claim 12, wherein the filleris at least one selected from the group consisting of clay, talc,silica, zeolite, zirconia, titania, and montmorillonite.
 14. Theadhesive film according to claim 12, wherein the adhesive layercomprises the filler in an amount of 1 to 50 parts by weight relative to100 parts by weight of the curable resin.
 15. The adhesive filmaccording to claim 1, wherein the adhesive layer further comprises acuring agent.
 16. The adhesive film according to claim 15, wherein thecuring agent is an amine-based compound, imidazole-based compound,phenol-based compound, phosphorus-based compound, or acidanhydride-based compound.
 17. The adhesive film according to claim 15,wherein the adhesive layer comprises the curing agent in an amount of 1to 10 parts by weight relative to 100 parts by weight of the curableresin.
 18. The adhesive film according to claim 1, wherein the adhesivelayer further comprises an initiator.
 19. The adhesive film according toclaim 1, wherein the adhesive layer further comprises a high molecularweight resin.
 20. The adhesive film according to claim 1, wherein thecurable adhesive layer has a single-layered structure or a multi-layeredstructure having at least two layers or more.
 21. An organic electronicdevice encapsulation product, comprising: a substrate; an organicelectronic device formed on the substrate; and an adhesive filmaccording to claim 1 encapsulating the organic electronic device,wherein the adhesive film covers an entire surface of the organicelectronic device.
 22. The organic electronic device encapsulationproduct according to claim 21, wherein the organic electronic device isan organic light emitting diode.
 23. A method for preparing an adhesivefilm encapsulating an organic electronic device OED, comprising a stepof storing the adhesive film at a temperature of −10° C. to 10° C.
 24. Amethod of encapsulating an organic electronic device OED, the methodcomprising: providing an adhesive film which comprises a curableadhesive layer comprising a curable resin, controlling a dimensionaltolerance (d) and edge angular tolerance (x) of the adhesive film tosatisfy Equation 1 or 2; applying the adhesive film, after controlling adimensional tolerance (d) and edge angular tolerance (x) to satisfyEquation 1 or 2, to a substrate on which the organic electronic deviceOED is formed to cover an entire surface of the organic electronicdevice OED:d=|df−di|<800 μm  [Equation 1]x=|xf−xi|<0.05 degrees  [Equation 2] where d_(i) is a length of a longerside or shorter side of the adhesive film at an optional i point, d_(f)is a length of a longer side or shorter side of the adhesive film at apoint of 2 weeks or more after the optional i point, x_(i) is an angleof an edge of the adhesive film at an optional i point, and x_(f) is anangle of an edge of the adhesive film at a point of 2 weeks or moreafter the optional i point.